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IS 3025-2 (2004): Methods of Sampling and Test (Physical

and Chemical) for Water and Waste Water, Part 2:
Determination of 33 Elements by Inductively Coupled Plasma
Atomic Emission Spectroscopy [CHD 32: Environmental
Protection and Waste Management]

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 IS 3025 (Part 2): 2004
ISO 11885:1996

Ylwlq R*) * Wi-Rril

m-J-12iR-u17@%rmmrfhmw
clGh-fim 33rrelmw?=n

Indian Standard
METHODS OF SAMPLING AND TEST (PHYSICAL >,*
AND CHEMICAL) FOR WATER AND WASTE WATER
PART 2 DETERMINATION OF 33 ELEMENTS BY INDUCTIVELY COUPLED PLASMA
ATOMIC EMISSION SPECTROSCOPY

ICS 13.060.50

@ BIS 2004
BUREAU OF INDIAN STANDARDS
MANAK BHAVAN, 9 BAHADUR SHAH ZAFAR MARG
NEW DELHI 110002
June 2004 Price Group 7
Environment Protection and Waste Management Sectional Committee, CHD 32

NATIONAL FOREWORD

This Indian Standard (Part 2) which is identical with ISO 11885:1996 Water quality Determination
of 33 elements by inductively coupled plasma atomic emission spectroscopy issued by the
International Organization for Standardization (ISO) was adopted by the Bureau of Indian Standards
on the recommendations of the Environment Protection and Waste Management Sectional Committee
and approval of the Chemical Division Council.

The text of ISO standard has been proposed to be approved as suitable for publication as an Indian
Standard without deviations. Certain conventions are, however, not identical to those used in Indian
Standards. Attention is particularly drawn to the following:

a) Wherever the words International Standard appears refemng to this standatti, they should be read
as Indian Standard,

b) Comma (,) has been used as a decimal marker tide in Indian Standatds, the current practice is to use
a point (.) as the decimal marker.

CROSS REFERENCES

In this adopted standard, reference appears to the following International Standard for which Indian
Standard also exists. The corresponding Indian Standard which is to be substituted in its place is
given below along with its degree of equivalence for the edition indicated:

hternational Standard Corresponding Indian Standard Degree of

Equivalence
ISO 5667-3 : 1994 Water quality IS 3025 (Part 1) : 1987 Methods of Technically
Sampling Part 3: Guidance on the sampling of test (physical and chemical) equivalent
preservation and handling of samples for water and wastewater: Part 1
Sampling (first revision)
 IS 3025 (Part 2] :2004
ISO 11885:1996

Indian Standard
METHODS OF SAMPLING AND TEST (PHYSICAL
AND CHEMICAL) FOR WATER AND WASTE WATER
PART 2 DETERMINATION OF 33 ELEMENTS BY INDUCTIVELY COUPLED PLASMA
ATOMIC EMISSION SPECTROSCOPY

1 Scope

1.1 Field of application

This International Standard specifies a method for the determination of dissolved, particulate or total elements in
raw, potable and waste water for the following elements:

aluminium, antimony, arsenic, barium, beryllium, bismuth, boron, cadmium, calcium, chromium, cobalt, copper,
iron, lead, lithium, magnesium, manganese, molybdenum, nickel, phosphorus, potassium, selenium, silicon,
silver, sodium, strontium, sulfur, tin, titanium, tungsten, vanadium, zinc, zirconium.

Table 1 lists these elements along with the recommended wavelengths and typical estimated instrumental detection
limits using conventional pneumatic nebulization. Actual working detection limits are sample-dependent and as the
sample matrix varies, these concentrations can also vary.

Because of the differences between various makes and models of satisfactory instruments, no detailed instrumental
operating instructions can be provided. Instead, the analyst will need to refer to the instructions provided by the
manufacturer of the particular instrument.

1.2 Interferences

Table 2 lists elements and the most important spectral interferences at the wavelengths recommended for analysis.

Several types of interference effects can contribute to inaccuracies in the determination of trace elements. They can
be summarized as follows.

a) Spectral interferences, categorized as:

1) overlap of a spectral line from another element; these effects can be compensated by utilizing computer
correction of the raw data;

2) unresolved overlap of molecular band spectra; these effects can possibly be overcome by selection of an
alternative wavelength.

If the appropriate equipment is available, wavelength scanning can be performed to detect potential spectral
interferences.

b) Background influences, categorized as:

2) background contribution from continuous or recombination phenomena;

3) background contribution from stray light from the line emission of elements in high concentration.

The effect of background interferences can usually be compensated by background correction adjacent to the
analyte line.

1
IS 3025 (Part 2) :2004
ISO 11885:1996

Table 1 Recommended wavelengths and typical detection Iimita

Wavelength Limit of detection Wavelength Limit of datection

Element Element
nm mg/1 nm mgil

Ag 328,068 0,02 Mo 202,030 0,03

338,289 0,02 204,598 0,05

Al 308,215 0,1 Na 589,592 0,1

396,152 0,1 588,995 0,02
167,08 0,04 330,237 0,02

As 193,696 0,1 Ni 231,604

197,197 0,1
189,042 0,08 P 178,287 0,5
213,618 0,1
B 208,959 0,005 214,914 0,1
249,678 0,006 177,428 0,5
247,773 0,01
Pb 220,353 0,2
Ba 233,527 0,004 283,306 0,07
455,403 0,002
493,409 0,003 s 182,036 0,5
313,042 0,002 180,689 0,5
234,861 0,005
313,107 Sb 206,833 0,1
217,581 0,1
Bi 223,061 0,04
306,772 0,08 Se 196,026 0,1
203,985 0,1
Ca 315,887 0,1
317,933 0,01 Si 251,611 0,02
393,366 0,002 212,412 0,02
288,158 0,03
Cd 214,438 0,01
226,502 0,01 Sn 235,848 0,1
228,802 0,01 189,980 0,1

co 228,616 0,01 Sr 407,771 0,0005

421,552 0,01
Cr 205,552 0,01 460,733 0,1
267,716 0,01
283,563 0,01 Ti 334,941 0,005
284,325 0,01 336,121 0,01
337,280 0,01
Cu 324,754 0,01 368,520 0,01
327,396 0,01
v 290,8!32 0,01
Fe 259,940 0,02 292,402 0,01
238,20 310,230 0,01
311,071 0,01
K 766,490
769,90 2 w 207,911 0,03
209,660 0,06
Li 460,286 0,9 239,709 0,06
670,764 0,002 222,589 0,06
202,998 0,06
Mg 279,079 0,03
279,553 0,0005 Zn 206,191 0,01
285,213 0,001 213,856 0,005

Mn 257,610 0,002 Zr 343,823 0,01

293,306 0,02 354,262 0,05
339,198

2
 IS 3025 [Part 2) :2004
ISO 11885:1996

Table 2 Spectral interferences

Wavelength Interfering Wavelength Interfering

Element Element
nm elements nm elements

Ag 328,066 Mo 202,030 Al, Fe

338,289 Cr 204,598

Al 308,215 Mn, V, Fe Na 589,592 Ar

396,152 Mo, cu 588,995
167,08 Fe 330,237

As 193,696 Fe, Al Ni 231,604 co

197,197 Fe, Al
189,042 Al P 178,287 I
213,618 Cu, Fe, Mo, Zn
B 208,959 Al, bto 214,914 Cu, Al, Mg
249,678 Fe, Cr 177,428 Cu
247,773 Fe
Pb 220,353 Al, co, Ti
Ba 233,527 Fe, V 283,306
455,403
493,409 s 182,036 Cr, Mo
313,042 v 180,669 Ca
234,861 Fe
313,107 Sb 206,833 Cr, Mg, Co, Mn
217,581
Bi 223,061 Cu
306,772 Fe, V Se 196,026
203,985
Ca 315,887 co
317,933 Fe, V Si 251,611
393,366 212,412
288,158
Cd 214,438 Fe
226,502 Fe Sn 235,848 Mo, co
228,802 As, co 189,980

co 228,616 Ti Sr 407,771
421,552
Cr 205,552 Fe, Mo 460,733
267,716 Mn, V
283,563 Fe, Mo Ti 334,941 Ca, Cr, Si
284,325 Fe 336,121
337,280
Cu 324,754 Ti. Fe 368,520 Co, Cr
327,396
v 290,882 Fe, Mo
Fe 259,940 292,402 Fe, Mo, Cr
238,20 co 310,230
311,071 Fe, Mn, Ti, Cr
K 766,490 Mg, Ar
769,90 w 207,911
209,860
Li 460,286 Fe 239,709
670,784 222,589 Cu
202,998
Mg 279,079
279,553 Zn 206,191 Cr
285,213 Fe 213,856 Cu, Ni, Fe

Mn 257,610 Fe, Mo, Cr Zr 343,823

293,306 Al, Fe 354,262
339,198

3
IS 3025 (Part 2) :2004
ISO 11885:1996

Physical interferences are generally considered to be effects associated with the sample nebulization and transport
processes. Such properties as change in viscosity and surface tension can cause significant inaccuracies,
especially in samples which may contain high concentrations of dissolved solids and/or acid. If these types of
interference are operative, they will be reduced by dilution of the sample and/or utilization of standard addition
techniques.

Chemical interferences are characterized by molecular compound formation, ionization effects and solute
vaporization effects. These effects are overcome by buffering of the sample matrix and by standard addition
procedures (see 8.1 .3.2).

Whenever a new or unusual sample matrix is encountered, a series of tests should be performed prior to reporting
concentration data for analyte elements. When investigating a new sample mat@x, comparison tests can be
performed using other analytical techniques, such as atomic absoqXion spectrometry.

Serial dilution If the analyte concentration is sufficiently high (minimally 10x the instrumental detection limit after
dilution), an analysis of a dilution needs to agree within 5 !4. of the original determination (or within some
acceptable control limit that has been established for that matrix). If not, a chemical or physical interference effect
could be responsible.

Calibration by standard addition (see 8.1.3.2) A spike added to the original determination at a minimum level of
10x the instrumental detection limit (maximum 100 x) needs to be recovered to within 80% to 110 %., or within the
established control limit for that matrix. If not, a matrix effect should be suspected. The use of a standard addition
analysis procedure can usually compensate for this effect.

2 Normative reference

The following standard contains provisions which, through reference in this text, constitute provisions of this
International Standard. At the time of publication, the edition indicated was valid. All standards are subject to
revision, and parties to agreements based on this standard are encouraged to investigate the possibility of applying
the most recent edition of the standard indicated below. Members of IEC and ISO maintain registers of currently
valid International Standards.

ISO 5667-3:1994, Water quality Sampling Pati 3: Guidance on the preservation and handling of samples.

3 Definitions

For the purposes of this International Standard, the following definitions apply:

3.1 dissolved metals:

Those metals in a water sample which will pass through a 0,45 ym membrane filter.

3.2 particulate metals:

Those metals in a water sample which are retained by a 0,45 ~m membrane filter.

3.3 total metals:

Concentration of metals determined on an unfiltered sample following digestion (see 8.1.3), or the sum of the
dissolved (see 8.1.1 ) plus particulate metal concentrations (see 8.1.2).

3.4 instrumental detection limit:

Concentration, equivalent to a signal due to the analyte, which is equal to three times the standard deviation of a
series of ten replicate measurements of a reagent blank signal at the same wavelength.

3.5 sensitivity:
Slope of the curve of the relationship between signal emission intensity and sample concentration.

3.6 instrument check standard:

Multielement standard of known concentrations prepared by the analyst to monitor and verify instrument
performance on a daily basis (see 5.7).

4
 IS 3025 (Part 21:2004
ISO 11885:1996

3.7 interference check sample:

Solution containing both interfering and analyte elements of known concentration that can be used to verify
background and interelement correction factors.

3.8 independent calibration check:

Solution, obtained from an outside source, having known concentration values to be used to verify the calibration
standards.

3.9 reference standards:

Series of known standard solutions used by the analyst for calibration of the instrument (i.e. preparation of the
calibration curve).

3.10 linear dynamic range:

Concentration range over which the analytical response remains linear.

3.11 reagent blank:

Deionized water, containing the same acid matrix as the calibration standards, which is carried through the entire
analytical scheme.

3.12 calibration blank:

Deionized water acidified with nitric or hydrochloric acid.

3.13 method of standard addition:

Analytical technique involving the use of the unknown analyte and the unknown analyte plus a known amount of
standard analyte (see 8.1.3.2).

3.14 sample duplication:

Analysis of two portions of the same sample.

4 Principle

The basis of the method is the measurement of atomic emission by an optical spectroscopic technique. Samples
are nebulized and the aerosol that is produced is transported to the plasma torch where excitation occurs.
Characteristic atomic-line emission spectra are produced by a radio-frequency inductively coupled plasma (ICP).
The spectra are dispersed by a grating spectrometer and the intensities of the lines are monitored by detectors.
The signals from the detectors are processed and controlled by a computer system. A background correction
technique is used to compensate for variable background contributions to the determination of trace elements.

5 Reagents

WARNING The toxicity of each reagent used in this method has not been precisely defined; however,
each chemical compound needs to be treated as a potential health hazard. From this viewpoint, exposure
to these chemicals to the lowest possible level by whatever means available is recommended.

Preparation methods involve the use of strong acids, which are corrosive and cause burns. Laboratory
coats, gioves and safety spectacles should be worn when handling acids.

Toxic fumes are evolved by nitric acid. Always carry out digestion in a fume cupboard, as well as addition
of acid to samples because of the possibility of toxic gases being released.

The exhaust gases from the plasma should be ducted away by an efficient fume extraction system.

5.1 General requirements

NOTE Standard stock solutions may be purchased Orprepared from ultrahigh-puritygrade chemicals.

The content of the determinants in the water and reagents shail be negligibly low, compared with the
concentrations to be determined.

5
IS 3025 (Part 2) :2004
ISO 11885:1996

All salts shall be dried for 1 h at 105 C unless otherwise specified.

5.2 Nitric acid, p(HNOJ = 1,40 g/ml

5.3 Dihydrogen dioxide (hydrogen peroxide), H,O,, volume fraction 30%.

NOTE On the determination of phosphorus, attention should be paid to a possible stabilization of hydrogen peroxide with
phosphoric acid, as this will affect the phosphorous determination.

5.4 Sulfuric acid, p(H,S04) = 1,84 g/ml.

5.5 Hydrochloric acid, cfHCl) = 0,2 mol/1.

5.6 Ammonium sulfate, (NH4)2S04.

5.7 Element stock solutions

Ag, Al, As, B, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Se, Si, Sn, Sr, Ti, V, W
and Zn at mass concentrations of 1000 mg/1each.

NOTE ICP-AES element standard reference solutions with respective specifications which can be used as stock solutions
are commercially available. They have been prepared according to particulars of the manufacturer. Normally, these stock
solutions contain hydrochloric acid or nitric acid and have a shelf life of several months. Formulations for the preparation of
element stock solutionsare identified below.

5.8 Intermediate mixed standard solutions

Prepare these as mixed element standards in 594 nitric acid or 5 % hydrochloric acid (volume fraction). To ensure
chemical compatibility use the combinations given in 5.8.1 to 5.8.6.

On composing multielement reference solutions, the chemical compatibility and the possible hydrolysis of the initial
compounds, as well as spectral interferences, shall be taken into account. In order to avoid interferences, the
digestion reagents (e.g. nitric acid, sulfuric acid, aqua regia) shall be added to the reference solutions.

5.8.1 Multielement reference solution 1

p(Al, Be, Cd, Co, Cu, Fe, Pb, Li, Mn, Mo, Ni, V, Zn, Bi, Si, Sr, W and Zr) = 10 mg/1.

Prepare this solution by adding (1O t 0,1) ml of each of the commercial 1000 mgl stock standard solutions (5.7) of
reference I elements in a 1-Iitre volumetric flask.

Add 50 ml of nitric acid (5.2).

Make up to the volume with water.

5.8.2 Multielement reference solution II

p(Sn, Ti, As, Se, Sb) = 10 mg/1.

Prepare this solution by adding (1O * 0,1 ) ml of each of the commercial 1000 mg/1stock standard solutions (5.7) of
reference II elements in a 1-Iitre volumetric flask.

Add 50 ml of nitric acid (5.2).

Make up to the volume with water.

5.8.3 Element reference solution Ill

p(Ba) = 10 mg/1.

Proceed as given in 5.8.2 using (1O * 0,1) ml of the commercial 1000 mg/i stock standard solution of barium.

6
 IS 3025 (Part 2) :2004
ISO 11885:1996

5.8.4 Element reference solution IV

p(Ag) = 10 mg/1.

Proceed as given in 5.8.2 using (1O* 0,1 ) ml of the commercial 1000 mg/1stock standard solution of silver.

5.8.5 Element reference solution V

P(B) = 10 mg/1.

Proceed as given in 5.8.2 using (10* 0,1) ml of the 1000 mgll stock standard solution of boron.

Prepare this standard in polymethylpentene (PMP) flasks.

NOTE Element reference solutions Ill, IV, V, i.e. Ba, Ag, B, are known to cause problems by precipitation under certain
circumstances,and it is recommended that separate standard solutionsare prepared.

5.8.6 Multielement reference solution VI

p (Ca, Mg, Na, K, S, P)= 10 mg/1.

Prepare this solution by adding (1O* 0,1) ml of each of the commercial 1000 mg/1 stock solutions (5.7) of
reference VI elements in a 1-Iitre volumetric flask.

Add 10 ml of nitric acid (5.2).

Make up to the volume with water.

5.9 Reagent blank solution

Place 1 ml of nitric acid (5.2) and 100 ml of water into a polyethylene or polytetrafluorethylene (PTFE) container.

6 Apparatus

NOTE Because of the differences between various makes and models of satisfactory instruments, no detailed operating
instructionscan be provided.

6.1 Inductively coupled plasma-atomic emission spectrometer, including:

computer-controlled atomic emission spectrometer with background correction;

radiofrequency generato~

argon gas supply (welding grade or better).

6.2 Sample bottles, 250 ml or 500 ml plastics (such as high density polyethylene or PTFE), for sample collection
and storage. Containers shall have been previously cleaned with 10 YO volume fraction nitric acid before use.

6.3 Glassware (beakers, filter funnels, volumetric flasks and pipettes) reserved for element preparation only. All
glassware shall be soaked in 10% volume fraction nitric acid overnight before use.

6.4 Acid dispensers, variable volume.

6.5 Membrane filtration equipment and filters of pore size 0,45 ~m reserved for element preparation.

7
IS 3025 (Part 2) :2004
ISO 11885:1996

7 Sample handling and preservation

7.1 General

The requirements in ISO 5667-3 apply.

For the determination of trace elements, contamination and the loss of elements of interest are of prime concern.
Dust in the laboratory environment, impurities in reagents and impurities on laboratory apparatus which the sample
contacts are all sources of potential contamination. Sample containers can introduce either positive or negative
errors in the measurement of trace elements by

a) leaching or surface resorption, and

b) by depleting concentrations through adsorption.

Laboratory glassware, including sample bottles, shall be rinsed before use with nitric acid followed by deionized
water.

Perform the following preservation and pretreatment steps (filtration and acid presewation) at the time the sample is
collected, or as soon as possible thereafter.

7.2 Prior to determination of dissolved elements

Filter the sample through a 0,45 ~m membrane filter (6.3.2) as soon as possible after collection (glass or PTFE
filtering apparatus are recommended to avoid possible contamination).

Use the first 50 ml to 100 ml to rinse the filter flask. Discard this portion and collect the required volume of filtrate.
Acidify the filtrate with 0,5 ml of nitric acid (5.2) per 100 ml of sample to ensure that the pH of the sample is< 2.

7.3 Prior to determination of particulate elements

Filter a measured volume of unpresewed sample through a 0,45 ~m membrane filter as soon as possible after
collection. Transfer the filter containing particulate material to a container for storage and/or shipment. No
preservative is required.

7.4 Prior to determination of total elements

Acidify the sample with 0,5 ml HNO, (5.2) per 100 ml sample to pH c 2 as soon as possible, preferably at the time of
collection. Do not filter the sample before processing.

8 Instrumental method and analytical procedure

8.1 Instrumental method

8.1.1 General

Follow the instructions provided by the manufacturer of the particular instrument.

NOTE Sensitivity, instrumental detection limit, precision, linear dynamic range and interference effects should be
investigated and established for each individualanalyte line on that particular instrument.

Set up the instrument with the proper operating parameters established from the manufacturers instruction manual.
Allow the instrument to become thermally stable before beginning.

Initiate the appropriate operating configuration of the computer.

Profile and calibrate the instrument according to the instrument manufacturer% recommended procedures, using the
typical mixed calibration standard solutions (5.8.1 to 5.8.6). Flush the system with the reagent blank (5.8.7) between
each standard.

8
 IS 3025 (Part 2) :2004
ISO 11885:1996

Before beginning the sample run, reanalyse the highest-concentration mixed reference standard as if it were a
sample. Ensure that the concentration values do not deviate from the actual values by more than *5% (or the
established control limits, whichever is lower). If they do, follow the recommendations of the instrument
manufacturer to correct for this condition.

Begin the sample run by flushing the system with the reagent blank (5.8.7) solution and flush again between each
sample. Analyse the instrument check standard (8.1.2) and the calibration blank every 10 samples.

8.1.2 Instrument performance check procedures

Analyse an appropriate instrument check standard containing the elements of interest with each batch of
10 samples. This check standard is used to determine instrument drift. If agreement is not within * 5 % of the
expected values or within the established control limits, whichever is lower, the analysis is out of control. Terminate
the analysis, correct the problem, and recalibrate the instrument.

Analyse the reference standard with each batch of 10 samples. The result shall be within the established control
limits of two standard deviations of the mean value. If not, repeat the analysis two more times and average the three
results. If the average is not within the control limit, terminate the analysis, correct the problem and recalibrate the
instrument.

To verify interelement and background correction factors, analyse the instrument check standard at the beginning,
end and at periodic intervals throughout the sample run. Results should fall within the established control limits of
2,0 times the standard deviation of the mean value. If not, terminate the analysis, correct the problem and
recalibrate the instrument.

8.1.3 Independent calibration check

8.1.3.1 General requirement

An independent calibration standard obtained from an outside source shall first be used for the initial verification of
the calibration standards. A fresh dilution of this sample shall be analysed every week thereafter to monitor their
stability. If the results are not within * 5 YO of the true value listed for the control sample, prepare a new calibration
standard and recalibrate the instrument. If this does not correct the problem, prepare a new stock standard and a
new calibration standard and repeat the calibration.

Prepare calibration check standards for all elements from stock solutions reserved for this purpose consisting of the
same matrix as the unknown samples and carried through the entire analytical process.

Analyse one calibration standard and one blank solution with each batch of 25 samples and take them through the
entire analytical processes (including dilution, filtering and digestion, etc.).

8.1.3.2 Standard addition method of analyais

NOTE The standard addition technique involves preparing new etandarde in the sample matrix by adding known amounts
of standard to one or more aliquots of the processed sample solution. This technique compensates for a sample constituent
that enhances or depresses the analyte signal, thus producinga different slope from that of the calibration standards. It will not
correctfor additive interference. The simplest veraion of this technique is the single-addtion method.

Take two identical aliquots of the sample solution, each of volume Vr To the first (Iabelled A) add a small volume Vs
of a standard analyte solution of concentration ps of the solvent. Measure the analytical signals of A and B and
correct for nonanalyte signals. Calculate the unknown sample concentration pXas follows:

sB,.vs.ps
= (S~-Se)Vx
where
S~, ~ are the analytical signals (corrected for the blank) of solutions A and B, respectively;

v- is the added volume of standard analyte, in millilitres;

Vx is the volume of identical aliquots of sample solution, in millilitres;

Ps k the mass concentration of standard analyte solution, in milligrams per Iitre.

9
is 3025 (Part 21:2004
ISO 11885:1996

Choose V~ and p~ so that S~ is on average twice Ss. It is best if Vs is made much less than Vxand thus ps is much
greater than pX, to avoid excess dilution of the sample matrix. If a separation or concentration step is used, first
make the addition and carry out the entire procedure. For the results from this technique to be valid, all of the
following requirements shall apply:

the analytical response shall be linea~

the chemical form of the analyte added shall respond the same as the analyte in the sample;

the interference effect shall be constant over the working range of concern;

the signal shall be corrected for any additive interference.

8.2 Analytical procedure

8.2.1 Determination of dissolved elements

Analyse the filtered, preserved sample (7.2) as-received in accordance with 8.1.1. The acid matrix and
concentration of the samples and calibration standards shall be the same. If a precipitate has formed upon
.
acidification of the sample or during transit or storage, it shall be redissolved before analysis by adding additional
acid and/or by heating on a hot plate.

8.2.2 Determination of particulate elements

Transfer the membrane filter containing the insoluble material (see 7.3) to a glass beaker and add 4 ml of nitric acid
(5.2). Cover the beaker with a watch glass and heat gently. The warm acid will soon dissolve the membrane.

Increase the temperature of the hot plate and digest the material. When the acid has nearly evaporated, cool the
beaker and watch glass and add another 3 ml of nitric acid (5.2). Cover and continue heating until the digestion is
complete, generally indicated by a Iight-coloured digestate. Evaporate to near dryness (2 ml), cool, add 10 ml of
hydrochloric acid (0,2 mol/1) and 15 ml of deionized, distilled water per 100 ml dilution and warm the beaker gently
for 15 min to dissolve any precipitated or residue material. Allow to cool, wash down the watch glass and beaker
wails with deionized or distilled water and filter the sample to remove insoluble material which can block the
nebulizer. Adjust the volume based on the expected concentrations of elements present. This volume will vary
depending on the elements to be determined. Analyse the sample in accordance with 8.1.1. Concentrations so
determined shall be reported as particulate.

NOTES

1 Instead of filtering, the sample after diluting and mixing may be centrifuged or allowed to settle by gravity overnight to
remove insoluble material.

2 Calibration standards/Analytical Quality Control solutionsshould be prepared at the same acid concentration.

3 A filter blank should be taken through the identical procedure as samples and subtracted from the sample analytical results
at the calculation stage.

8.2.3 Determination of total elements

Acidify 100 ml of sample (see 7.4) with 0,5 ml of nitric acid (5.2).

Evaporate the mixture to near dryness, making sure that no area at the bottom of the beaker goes dry (a complete
drying may lead to low results).

In case of an incomplete digestion (undissolved material), add some water and repeat the treatment.

Dissolve the residue in 1 ml of nitric acid (5.2) and some water and make up to 100 ml volume with water. Analyse
the resulting solution in accordance with 8.1.1.

NOTE Some elements or their compounds (e.g. antimony, silicon, alumina, tin, titanium) are only partially dissolved by this
digestion procedure and care should be taken in the interpretationof results.

10
 IS 3025 (Part 2) :2004
ISO 11885:1996

9 Calculation andexpression of results

Subtract reagent blanks from all samples. This is particularly important for digested samples requiring large
quantities of acids to complete the digestion.

If dilutions were performed, apply the appropriate factor to the sample values.

Report results in milligrams (or micrograms) of element per Iitre of sample and up to three significant figures.

10 Precision

Typical performance characteristics for precision and accuracy are shown in Table 3.

Details of an interlaboratory test on the precision of the method are summarized in annex A. The values derived
from this interlaboratory test may not be applicable to concentration ranges and matrices other than those given.

11 Test report

The test report shall contain the following information:

a) a reference to this International Standard;

b) a reference to the method used;

c) complete identification of the sample;

d) the results of the determinations;

e) any details not specified in this International Standard or which are optional, as well as any factors which may
have affected the results.

11
IS 3025 (Part 2) :2004
ISO 11885: 1996

Table 3 Typical precision and accuracy data

True value Mean reporkd value Mean percent

Element
pgll /1g/1 RSD = Vc

Aluminium 50 51,8 4,3

Barium 2500 2450 3,8
Beryllium 500 488 3,1
Boron 500 490 3,5
Cadmium 50 51,0 2,8
Calcium 2000 20878 6,0
Chromium 50 50,3 3,3
Copper 50 49,6 5,1
Iron 50 50,5 5,0
Lead 100 101,4 2,6
Magnesium 2000 2103 6,0
Manganese 50 49,9 2,7
Nickel 50 51,6 3,3
Phosphorus 5000 4923 1,7
Potassium 1000 1000 10,6
Sodium 2000 2035 9,7
Sulfur 20000 19988 5,1
Titanium 500 491 4,2
Vanadium 500 510 6,3
Zinc 50 49,0 5,4

12
 IS 3025 (Part 2) ; 2004
ISO 11885:1996

Annex A
(informative)

Results of an interlaboratory trial

A national interlaboratorv trial was performed in January 1987 in order to compare the repeatability and the
reproducibility of the methods. These results are summarized in table A.1.

Table A.1 Statistical characteristics of the method Standard solutions

Parameter Element
B Ca Cd Cu Fe Mg Mn Mo Na P Se Ti v Zn

No. participating 23 25 21 24 26 25 19 22 21 20 21 22 23 24
laboratories
No. measuring 83 90 72 91 95 91 69 80 80 75 76 81 87 90
values
Reference values 3,5 34,5 0,1 0,7 2,5 25,0 0,25 0,5 15,0 6,52 9,0 5,5 0,5 1,3
[mg/1)
Mean (mg/1) 3,5 34,86 0,098 0,670 2,546 24,93 0,241 0,494 15,07 6,820 8,931 5,449 0,495 1,302

Repeatability:
Standard 0,058 0,817 0,003 0,012 0,045 0,391 0,003 0,017 0,331 0,210 0,177 0,086 0,017 0,024
deviation o,
Coefficientof 1,6 2,3 2,9 1,8 1,8 1,6 1,4 3,3 2,2 3,1 2,0 1,6 3,5 1,8
variationCV,

Reproducibility:
Standard 0,176 2,112 0,004 0,034 0,118 0,766 0,007 0,026 0,857 0,374 0,474 0,247 0,039 0,058
deviation aR
Coefficientof 5,0 6,1 4,5 5,1 4,6 3,1 2,7 5,2 5,7 5,5 4,2 4,5 7,9 4,5
variationCVR

% Recovery 100 101,1 97,7 95,7 101,9 99,7 96,5 98,8 100,5 100,4 99,2 99,1 99,0 100,1

13
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